Compositions containing tall oil pitch and epoxy ether resins



United States Patent "ice Patented May 20, 1969 3 445 409 It is afurther object of the present invention to provide COMPOSITIONS 'f TALLOIL PITCH an extended epoxy ether resin composition in which the ANDEPOXY ETHER RESINS extender 1s a by-product of lim ted known commercialVincent Francis DAgostino, South Huntington, N.Y., 25- lue, whichextender is compatible with such reslns 01 signor, by mesne assignments,to Arizona Chemical may be readily rendered so. Company, New York, N.Y.,a corporation of Delaware 5 Another object of this invention Is toprovide an ex- No Drawillg- Continuation-infill lfp tended epoxy etherresin composition in which the exg fi g 1963- This appllcatloll 1966,tender will not sweat out or tend to separate therefrom upon curing ofthe resin mixture.

Us Cl Cosg 45/00 45/12 4 Claims These and other objects and advantageswill be ap- 10 parent from the description of the present invention setforth hereinbeloW.

In accordance with the present invention, compositions ABSTRACT OF THEDISCLOSURE are provided which comprise an epoxy ether resin An epoxyresin composition consists essentially of a characterized by an epoxyequivalence greater than 1, an heat-cured blend of an epoxy ether resin,an amide of a amine containing polyamide having an amine equivalencepolymeric fatty acid with an aliphatic polyamine, and a greater than 2and tall oil pitch. tall oil pitch containing about equal parts of fattyacids, The epoxy ether resin will be present in the composition rosinacids, and unsaponifiables. based on 100 parts of a mixture of saidresin and said tall oil pitch of from about to about 80 parts of epoxy2O resin to 80 parts to about 20 parts of tall oil pitch. Thisapplication is a continuation-in-part of application Preferably, theepoxy ether resin will be employed in Ser. No. 282,600 filed May 23,1963, now abandoned. amounts of from between 80 and 40 parts while thetall The present invention relates to novel resinous comoil pitch willbe employed in amounts of from between positions suitable for use incasting and potting. More about 20 and 60 parts.

particularly, the present invention relates to novel resinous The epoxyethers or resins suitable for use in the comcompositions containing talloil pitch and epoxy ether positions of this invention contain glycidylether groups resins, which compositions are suited for use in formuandare characterized by a 1, 2-epoxy equivalency in the lating calkingcompounds for preparing road beds of average molecule of greater than 1and usually about 2. improved properties, for casting and potting, andespecial- By epoxy equivalency, reference is made to the average ly forpreparing castings and pottings characterized by number of 1, Z-epoxygroups contained in the average good electrical properties. molecule ofthe ether.

Epoxy ether resins in general may be said to form tough A preferredgroup of epoxy ethers contemplated for polymers of good electricalresistance. These polymers use in this invention is prepared by reactinga dihydric are employed extensively as adhesive, casting, potting,phenol with epichlorohydrin in alkaline solution. These cement patchingand coating resins. Their high cost howproducts are in general viscousliquids at normal temperaever, prevents their adaptation for some usersWhere they tures, i.e., room temperature. Illustrative of the mightotherwise be employed. various dihydric phenols useful in preparingthese glycidyl While various extenders or diluents have been incorethersare the mononuclear phenols, like resorcinol, cateporated into epoxyether resins heretofore for purposes 4 chol, hydroquinone and the like;polynuclear phenols of reducing the cost of the resin, the incorporationof such like bis-(4-hydroxyphenyl)-2,2-propane frequently identidiluentsfor the most part dramatically and adversely affied as bis-phenol A,4,4- dihydroxybenzophenone, bis-(4- fects important characterizingproperties of epoxy ether hydroxyphenyl)-1,1-ethane,bis-(4-hydroxyphenyl) 1,1- resin. Further, many potential diluments areincompatible isobutane, bis-(4-hydroxy-2-methylphenyl)-2,2-propane, withepoxy ether resins or are at best rendered compatible bis (2dihydroxynaphthyl) methane, 1,5 dihydroxywith great difficulty.Normally, inorganic materials are 4 naphthalene and the like.

incorporated to modify physical properties. These mate- Suitable epoxyether resins may be represented by the rials are not dissolved in thepolyepoxide, they meregeneral formula CH;-OHCH -(OR-O-C HzCHOHC H2)n0R0CH2CH-CH1 1y serve to add bulk and improve mechanical propwhere thevalue of n is from 0 to 7, R is a divalent hydroerties such asmachinability. Typically, the incorporacarbon radical of a dihydricphenol. The preferred phenol tion of such materials as silica or tale insubstantial is bis-phenol A.

amounts in epoxy ether resin coating compositions will Other epoxyethers contemplated include the polyglyadversely affect the rate of cureand the toughness and cidyl ethers of polyhydric alcohols such as thediglycidyl strength of the finish. In addition, the incorporation ofether of enthylene glycol, propylene glycol, diethylene,

some diluents or extenders, particularly in substantial glycol, mannitoland the like. amounts, will so adversely affect the electricalresistance Tall oil pitch is a product of somewhat varied comof epoxyresins as to render them unsuited for some uses position, dependent tosome extent upon its source and such as in some pottings and castingswhere electrical processing conditions. Tall oil pitch typically is adark properties are important. brown (Gardner Color-193350% in benzene12-15) Accordingly, it is a principal object of the present inproductobtained from the fractionation of tall oil. Thus, vention to providecompatible extended epoxy resin ether in the production of distilledtall oil, tall oil rosin, and compositions which may be cast and pottedand which, tall oil fatty acids, a crude tall oil is subjected tocontinwhen so cast and potted, are physically tough, easily mauousfractional distillation employing equipment and prochined andcharacterized by good electrical properties. cedures similar to thoseemployed in the refining of petroleum. The crude tall oil enters afractionating tower to remove high boiling constituents. These arewithdrawn from the bottom of the fractionating tower and constitute thetall oil pitch contemplated for use in this invention. Normally, suchpitch will contain about as ethylene diamine, diethylcne triamine,though these materials may be employed also if desired.

As noted above, various solvents may be employed to dilute thecompositions of this invention and render them more workable. Suchsolvents include the convenequal parts of fatty, acids, rosin acids andunsaponifiable tional hydrocarbon solvents such as naphtha, benzene,matter. Illustratively, such a pitch may contain 29% fatty xylenes, thechlorinated hydrocarbons, and even the use acids, 31% rosin acids and33% unsaponifiable matter. of reactive diluents such as styrene oxideare contem- These acids include esterified ,acids. Tall oil pitch has aplated. lighter color than other available pitches and thus is In orderto illustrate the present invention, the followuniquely applicable incasting and potting areas when ing examples are given primarily by wayof illustration. compared with other commercial pitches. It is solublefor No specific details or enumerations contained therein the most partin petroleum and aromatic solvents, thus should be construed aslimitations on the present invention facilitating its use as a diluentin accordance with the except insofar as they appear in the appendedclaims. present invention. In Table I hereinbelow, reference is made tocom- In addition to tall oil pitch, epoxy ether and, if desired, apatibility. This test was carried out by simply mixing the variousinorganic fillers and solvent vehicles, a curing materials reported inTable I in a test tube. If a single agent for the epoxy ether resin willnormally be employed. clear phase resulted, the materials wereconsidered com- The amine containing polyamides or polyaminepolyapatible and sheets were cast for testing. As noted earlier, midescontemplated for use in this invention are conif materials areincompatible they are expressed or sweat densation products of polymericfatty acids with aliphatic out during curing of the resin and adverselyaffect the polyamines. Typically, these polyamides are soft resinousproperties of the final product. materials which may be described asviscous liquid. In preparing the castings for testing, the epoxide etherMaterials of this general type are disclosed in US. Pat. resin, thecuring agent and the tall oil pitch were blended 2,450,940, and those ofmore particular importance to at room temperature so that a minimum ofair was enthis invention in US. Pat. 2,705,223, and in particulartrapped. The blend was then placed in a vacuum desicin column 2, linesthrough 60 thereof. Typically, such cator in a large bottle and thepressure reduced to about polyamides may be prepared according to theprocess 1 millimeter. The blend foamed and care was exercised describedin US. Pat. 2,379,413 from commercially availso that the foam remainedwithin the bottle. After a brief able dimer acids (prepared from longchain l220 carbon 30 period, further air was not released and the foamwas atom unsaturated fatty acid) such as dioleic or dilinoleiccollapsed. including the dimer acids of mixtures of these acids suchThese blends were then cast into sheets of approxias are found incommercially available tall oil fatty acid, mately A1 inch in thicknessby casting the blend into a and polyfunctional amines such as diethylenetriamine, suitable cavity and curing at 80 C. for two hours. methylene\ietramine, in Such a ratio as to P p The samples after casting wereevaluated for gross Polymeric material With an excess of amine pphysical properties and for electrical properties.

The amine containing polyamide is normally employed in the compositionson the basis of approximately one EXAMPLES active amine group to oneactive epoxide group, since Examples 1-9 were carried out in accordancewith an excess of epoxide normally results in a waste of active theprocedure described above employing the components material while anexcess of amine results in an alkaline identified in Table I in theamounts there reported.

TABLE I.Compatible Formulations Examples 1 2 3 4 5 6 7 8 9 EpoxideADiethylenetriamine Polyamide-Po1yamine Resin L Epoxide B 4 gall OilPitchl Antifoaming agent used as 1% in polyamide-polyamine resin whennecessary.

2 Bis glycidyl ether of his phenol A, i.e., 2,

2-bis(4-glyeidyloxy)phenyl) propane.

8 Dimer acid of tall oil fatty acids (essentially a 1:1 mixture of oleicand linoleic acid) reacted with diethylene triamine. This resin has anamine termmed with a Brookfield Viseometer Model RVF at 75 value of 345,a viscosity as de- C. of 8 poises, a percent ash by weight of 0.01%, aspecific gravity 25 C./25 C. of 0.97, weighs 8.1 pounds gallon at 25 C.

C. ASTM D92 of 265 C. The amine value reported is the number of 5 I 5 2HrS., 80 C.

product which for many purposes is undesirable. A range of .81.2 to lamine groups of epoxy group is suitable for most compositionscontemplated by this invention. For the most part, the amine group toepoxy group ratio can also be expressed in terms of relative weightratios. Thus, preferably the amine containing polyamide and the epoxyether resin are employed in relative weight ratios of about 1 to i,thought weight ratios of from about .8 to about 1.2 to 1, respectively,may be employed.

The latitude in the relative ratio of amine group and epoxy group isprimarliy due to the fact that the tall oil pitch contains some carboxygroups which are reactive with the epoxy groups and for that matter withamine groups.

In addition to resulting in compatible compositions, thepolyamine-polyamides are curing agents for the epoxide ethers and thusthe compositions of this invention do not require the use ofconventional amine curing agents such Table I demonstrates that tall oilpitch is compatible with epoxy ether resins over a relatively widerange. In the formulas of Examples 3-5 the pitch is brought intosolution with the epoxy ether resin by means of the polyamide polyamineresin. The qualitative properties of the formulations of thse examplesappear good, as will be seen hereinafter. Employing pitch at a 33% levelproduced a product having excellent properties, as will be evident fromthe test data presented hereinafter. As the amount of pitch isincreased, Examples 4 and 5, gross physical properties fall off.

Three formulations identical with that of Example 1, but containing 37,113.5 and 341 parts of tall oil pitch were incompatible and were notcured.

Sample castings of those prepared in selected examples reported in TableI were further tested for electrical and and epichlorohydrin in analkaline solution, and the polyamide-polyamine curing agent hasapproximately an active TABLE IL-ELECTRICAL PROPERTIES OF PITCH-EPOXYBLENDS AND CONTROLS Dielectric Constant I Thickness, Surface, u Volume,c 60, 10, Sample mils. ohm/em. ohm/em. Surface b 0 Volume b v c.p.s.e.p.s. c.p.s

Cast from Formula 0! Example 1 144 5. 8X10" 1. 6X10" 4. 6X10" 9. 4x10"i: Cast from Formula 01 Example 2 133 10x10 1. 3x10" 7. 0x10" 5. 0x10"21 g: Cast trom Formula 0! Example 3 133 1. 0x10 3. 3x10 3. 4x10 1. 1 103 08 Dissipation Factor 60, 10', 10, Thickness, Short Time I Water, absSample e.p.s. c.p.s. e.p.s. mils. Break-down, kv. Volts/mil. percent 14653 363 Cast from Formula oi Example 1 0027 8' 882: 3' 83 146 54 370 1253 363 67 500 0.0054 0 0002 0 022 Cast (rom Formula 01 Example 2 137 69504 33 wax-,1." 2323 3322 a? 22 a 4 Cast from Formula 01 Example 3 on019 130 65 500 D 44 l 40 hrs. at 23 0., 50% relative humidity. bCondition 1 plus 96 hrs. at 35 0., 90% relative humidity. Impressedvoltage: 500.

The physical test results on selected samples are set forth in Table IIIbelow.

TABLE TIL-PHYSICAL TEST RESULTS SAMPLE CAST FROM FORMULA Tables 11 andIII above demonstrate that the pitch filled epoxy ether resins arecharacterized by good strength properties and that in fact theirelectrical properties are improved. The low dielectric constant showsthe reduced polarity of resins obtained by the addition of tall oilpitch.

I claim:

1. An epoxy resin consisting essentially of the product obtained bypreparing a uniform blend of about 80 to 120 parts by weight of theamide of polymeric higher fatty acids with excess aliphatic polyaminesand about 25 to 400 parts by weight of a tall oil pitch containing aboutequal parts of fatty acids, rosin acids and unsaponifiables and having aGardner color of 12-15 when measured in a 50% solution in benzene,admixing said blend uniformly with about 100 parts by weight of an epoxyether resin having an epoxy equivalence greater than 1, and heat-curingthe mixture.

2. A composition according to claim 1 in which the epoxide resin isprepared by reacting a dihydric phenol References Cited UNITED STATESPATENTS 3,277,052 10/ 1966 Thompson et al 26028 3,190,845 6/1965Goodnight 26028 2,824,078 2/1958 Mellick 26028 FOREIGN PATENTS 230,1418/ 1960 Australia. 884,624 12/ 1961 Great Britain.

OTHER REFERENCES Asphalts and Allied Substances, vol. I, 5th ed.,

Abraham, Van Nostrand, 1945, pp. 402-403.

DONALD E. CZAJA, Primary Examiner.

C. WARREN IVY, Assistant Examiner.

US. CI. X.R.

